Enhanced Intrinsic Self-Healing Performance of Mussel Inspired Coating via In-Situ Cation Capture.

Under damp or aquatic conditions, the corrosion products deposited on micro-cracks/pore sites bring about the failure of intrinsically healable organic coatings. Inspired by mussels, a composite coating of poly (methyl methacrylate-co-butyl acylate-co-dopamine acrylamide)/phenylalanine-functionalized boron nitride (PMBD/BN-Phe) is successfully prepared on the reinforcing steel, which exhibits excellent anti-corrosion and underwater self-healing capabilities. The self-healing property of PMBD is derived from the synergistic effect of hydrogen bonding and metal-ligand coordination bonding, and thereby the continuous generation of corrosion products can be significantly suppressed through in situ capture of cations by the catechol group. Furthermore, the corrosion protection ability can be remarkably improved by the labyrinth effect of BN and the inhibition role of Phe, and the desired interfacial compatibility can be formed by the hydrogen bonds between BN-Phe and PMBD matrix. The corrosion current density (icorr) of PMBD/BN-Phe coating is determined as 7.95 × 10-11 A cm-2. The low-frequency impedance modulus (|Z|f  =  0.0 1 Hz is remained at 3.47 × 109 Ω cm2, indicating an ultra-high self-healing efficiency (≈89.5%). It is anticipated to provide a unique strategy for development of an underwater self-healing coating and robust durability for application in anti-corrosion engineering of marine buildings.

Gold Nanoparticles as Effective ion Traps in Poly(dimethylsiloxane) Cross-Linked by Metal-Ligand Coordination.

At this time, the development of advanced elastic dielectric materials for use in organic devices, particularly in organic field-effect transistors, is of considerable interest to the scientific community. In the present work, flexible poly(dimethylsiloxane) (PDMS) specimens cross-linked by means of ZnCl2-bipyridine coordination with an addition of 0.001 wt. %, 0.0025 wt. %, 0.005 wt. %, 0.04 wt. %, 0.2 wt. %, and 0.4 wt. % of gold nanoparticles (AuNPs) were prepared in order to understand the effect of AuNPs on the electrical properties of the composite materials formed. The broadband dielectric spectroscopy measurements revealed one order of magnitude decrease in loss tangent, compared to the coordinated system, upon an introduction of 0.001 wt. % of AuNPs into the polymeric matrix. An introduction of AuNPs causes damping of conductivity within the low-temperature range investigated. These effects can be explained as a result of trapping the Cl- counter ions by the nanoparticles. The study has shown that even a very low concentration of AuNPs (0.001 wt. %) still brings about effective trapping of Cl- counter anions, therefore improving the dielectric properties of the investigated systems. The modification proposed reveals new perspectives for using AuNPs in polymers cross-linked by metal-ligand coordination systems.

Weak Coordinating Character of Organosulfonates in Oriented Silica Films: An Efficient Approach for Immobilizing Cationic Metal-Transition Complexes.

Iron (II) tris(2,2'-bipyridine) complexes, [Fe(bpy)3]2+, have been synthesized and immobilized in organosulfonate-functionalized nanostructured silica thin films taking advantage of the stabilization of [Fe(H2O)6]2+ species by hydrogen bonds to the anionic sulfonate moieties grafted to the silica nanopores. In a first step, thiol-based silica films have been electrochemically generated on indium tin oxide (ITO) substrates by co-condensation of 3-mercaptopropyltrimethoxysilane (MPTMS) and tetraethoxysilane (TEOS). Secondly, the thiol function has been modified to sulfonate by chemical oxidation using hydrogen peroxide in acidic medium as an oxidizing agent. The immobilization of [Fe(bpy)3]2+ complexes has been performed in situ in two consecutive steps: (i) impregnation of the sulfonate functionalized silica films in an aqueous solution of iron (II) sulfate heptahydrate; (ii) dipping of the iron-containing mesostructures in a solution of bipyridine ligands in acetonitrile. The in situ formation of the [Fe(bpy)3]2+ complex is evidenced by its characteristic optical absorption spectrum, and elemental composition analysis using X-ray photoelectron spectroscopy. The measured optical and electrochemical properties of immobilized [Fe(bpy)3]2+ complexes are not altered by confinement in the nanostructured silica thin film.

Self-Healing Metallo-Supramolecular Hydrogel Based on Specific Ni2+ Coordination Interactions of Poly(ethylene glycol) with Bistriazole Pyridine Ligands in the Main Chain.

In this study, a supramolecular hydrogel formed by incorporating the 2,6-bis(1,2,3-triazol-4-yl)-pyridine (btp) ligand in the backbone of a polymer prepared by copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) "click" polyaddition reaction of 2,6-diethynylpyridine and diazido-poly(ethylene glycol) is reported. The hydrogelation is selectively triggered by the addition of Ni2+ ions to aqueous copolymer solutions. The gelation and rheological properties could be tuned by the change of metal to ligand ratio and polymer concentration. Interestingly, the hydrogel exhibits a fast (within 2 min) and excellent repeatable autonomic healing capacity without external stimuli. This self-healing behavior may find potential applications for the repairing of metal coatings, in the future.

Metal Ion Selective Self-Assembly of a Ligand Functionalized Polymer into [1+1] Macrocyclic and Supramolecular Polymer Structures via Metal-Ligand Coordination.

The design and synthesis of polymer-based metallomacrocycles relying on metal-ligand interactions remain a challenge in the polymer field. Instead of utilizing chemical reactions to synthesize macrocycles, a general approach is proposed to construct metallomacrocyclic structures through supramolecular self-assembly of a specific macroligand with suitable transition metal ions. Therefore, a new ditopic macroligand (L) consisting of PEG end-capped with 2,6-bis(1,2,3-triazol-4-yl)pyridine derivatives is prepared via CuAAC "click" reaction. Four types of metal (Fe2+ , Zn2+ , Ni2+ , and Cu2+ ) complexes are obtained by simply mixing a solution of metal ions and L in appropriate concentrations. The investigation of the coordination chemistry suggests that coordination of L with Cu2+ results in the formation of a [1+1] metallomacrocycle, while the other metal complexes exclusively lead to the formation of linear metallopolymers and/or larger aggregates. This work provides new insights into designing metallomacrocycles and may have potential application in the synthesis of catenanes and other cyclic or cycle-based topological architectures.

Bioinspired Synergistic Fluorescence-Color-Switchable Polymeric Hydrogel Actuators.

Many living organisms have amazing control over their color, shape, and morphology for camouflage, communication, and even reproduction in response to interplay between environmental stimuli. Such interesting phenomena inspire scientists to develop smart soft actuators/robotics via integrating color-changing functionality based on polymer films or elastomers. However, there has been no significant progress in synergistic color-changing and shape-morphing capabilities of life-like material systems such as hydrogels. Herein, we reported a new class of bioinspired synergistic fluorescence-color-switchable polymeric hydrogel actuators based on supramolecular dynamic metal-ligand coordination. Artificial hydrogel apricot flowers and chameleons have been fabricated for the first time, in which simultaneous color-changing and shape-morphing behaviors are controlled by the subtle interplay between acidity/alkalinity, metal ions, and temperature. This work has made color-changeable soft machines accessible and is expected to hold wide potential applications in biomimetic soft robotics, biological sensors, and camouflage.

Self-Healing Sensors Based on Dual Noncovalent Network Elastomer for Human Motion Monitoring.

Nowadays, it is still a challenge to prepare flexible sensors with great mechanical strength, stretchability, high sensitivities, and excellent self-healing (SH) abilities. Herein, a nanostructured supramolecular elastomer is reported with a dual noncovalent network of hydrogen bonding interactions and metal-ligand coordination. The resultant flexible sensor presents ultrafast (30 s), autonomous, and repeatable SH ability with high healing efficiency (80% after the 3rd healing process), as well as enhanced mechanical properties. Benefitting from the 3D conductive network, the sensor exhibits high electrical sensitivity and very low detection limit (0.2% strain). As a result, the flexible sensor is capable of precisely monitoring small strains of human motions (such as vocal-cord vibration), and exhibits reproducible and recognizable current signals after cutting-healing process. The dual noncovalent network design proposed here opens up a new opportunity for scalable fabrication of high performance SH sensors and other electronic devices.

Low-temperature, ultra-fast, and recyclable self-healing nanocomposites reinforced with non-solvent silylated modified cellulose nanocrystals.

Developing polymeric materials with remarkable mechanical properties and fast self-healing performance even at low temperatures is challenging. Herein, the polymeric nanocomposites containing silane-treated cellulose nanocrystals (SCNC) with ultrafast self-healing and exceptional mechanical characteristics were developed even at low temperatures. First, CNC is modified with a cyclic silane coupling agent using an eco-friendly chemical vapor deposition method. The nanocomposite was then fabricated by blending SCNC with matrix prepolymer, prepared from monomers that possess lower critical solution temperature, followed by the inclusion of dibutyltin dilaurate and hexamethylene diisocyanate. The self-healing capability of the novel SCNC/polymer nanocomposites was enhanced remarkably by increasing the content of SCNC (0-3 wt%) and reaching (≥99 %) at temperatures (5 & 25 °C) within <20 min. Moreover, SCNC-3 showed a toughness of (2498 MJ/m3) and SCNC-5 displayed a robust tensile strength of (22.94 ± 0.4 MPa) whereas SCNC-0 exhibited a lower tensile strength (7.4 ± 03 MPa) and toughness of (958 MJ/m3). Additionally, the nanocomposites retain their original mechanical properties after healing at temperatures (5 & 25 °C) owing to the formation of hydrogen bonds via incorporation of the SCNC. These novel SCNC-based self-healable nanocomposites with tunable mechanical properties offer novel insight into preparing damage and temperature-responsive flexible and wearable devices.

Metal ion-manipulated afterglow on rhodamine 6G derivative-doped room-temperature phosphorescent PVA films.

The long-lived room-temperature phosphorescence (RTP) originating from thiophene boronate polyvinyl alcohol (PVA) has enabled the creation of metal-ion-responsive RTP films doped with spirolactam ring-containing rhodamine 6G (1). In this study, RTP-active PVA films, namely, TDB@PVA and ATB@PVA, were prepared through boronate esterification of thiophene-2,5-diboronic acid (TDB) and 5-acetylthiophene-2-boronic acid (ATB) with the diol units of PVA. The delayed emission properties were evaluated, revealing an emission band at 477 nm with a turquoise afterglow for TDB@PVA and at 510 nm with a green afterglow for ATB@PVA after UV light irradiation ceased. The photophysical properties were assessed using TD-DFT and DFT calculations at the B3LYP/cc-pVDZ level. N-(rhodamine-6G)lactam dye with a salicylimine unit (1) was doped into the RTP-based PVA films, producing a multicolored afterglow upon the addition of metal ions. This phenomenon is explained by a triplet-to-singlet Förster-type resonance energy transfer process from the cross-linked thiophene boronate in PVA to the metal-ion-activated colored form of 1. This photophysical feature finds applicability in encryption techniques. Notably, the reversible metal-ligand coordination of 1 in the PVA system enabled a write/erase information process.

Dynamic Metal-ligand Coordination for Fluorescence Color Regulation of Hydrazone-based Bistable Photoswitches.

Achieving effective manipulation of emission color in photoresponsive materials is crucial for various advanced photonic applications. In this study, we designed and synthesized a hydrazone compound 1, ethyl (Z)-2-(2-([2,2':6',2''-terpyridin]-4'-yl)hydrazineylidene)-2-(4-(diphenylamino)phenyl)acetate, which possesses a push-pull structure incorporating triphenylamine and terpyridine. The emission intensity of compound 1 can be repeatedly switched "off" and "on" by irradiation with visible light and UV light, which induces the isomerization transition between the Z and E forms. In addition, compound 1 is capable of changing its emission wavelength from 540 nm to 607 nm through coordination with different zinc salts in toluene/CH2 Cl2 mixture (v : v=1 : 1). Importantly, we have successfully achieved dynamic manipulation of fluorescence color and intensity by altering the counterions of zinc complexes and switching the isomer from Z to E. Moreover, both compound 1 and its zinc complexes demonstrate remarkable photoswitchable properties with different fluorescence colors in the thin films. Finally, these films with various fluorescence colors were used for the production of luminescent tags.

Enzymatically mediated Gleditsia sinensis galactomannan based hydrogel inspired by wound healing process.

The self-healing property based on metal-ligand physical coordination is particularly interesting in bio-hydrogel science due to its allowance for multiple local healing events to process. As the most abundant renewable green resource in nature, Gleditsia sinensis galactomannan has great potential as a starting material for functional materials. In this study, the biocompatible Gleditsia sinensis galactomannan and cellulose were firstly chemically modified and then taken as the main constituent for constructing the metal-ligand coordination through an enzyme-regulated strategy. The hydrogel could quickly gelatinize in the surrounding environment, corresponding to the violent exothermic phenomenon, and exhibit extraordinary self-healing behavior. The molecular dynamics simulation of the hydrogel confirmed the more stable coordinated configuration from Fe(III)-chelates than Fe(II)-chelates. The morphology, mechanical property, antibacterial, and cytotoxicity of the prepared hydrogel were also studied. Our results indicated that galactomannan hydrogel based on the metal-ligand networks could balance the kinetic stability and intrinsic healability through the enzyme-induced route, which provide a new perspective in the field of biomaterial applications.

Self-Healing of Polymers and Polymer Composites.

This review is devoted to the description of methods for the self-healing of polymers, polymer composites, and coatings. The self-healing of damages that occur during the operation of the corresponding structures makes it possible to extend the service life of the latter, and in this case, the problem of saving non-renewable resources is simultaneously solved. Two strategies are considered: (a) creating reversible crosslinks in the thermoplastic and (b) introducing a healing agent into cracks. Bond exchange reactions in network polymers (a) proceed as a dissociative process, in which crosslinks are split into their constituent reactive fragments with subsequent regeneration, or as an associative process, the limiting stage of which is the interaction of the reactive end group and the crosslink. The latter process is implemented in vitrimers. Strategy (b) is associated with the use of containers (hollow glass fibers, capsules, microvessels) that burst under the action of a crack. Particular attention is paid to self-healing processes in metallopolymer systems.

Swelling and Mechanical Properties of Polyacrylamide-Derivative Dual-Crosslink Hydrogels Having Metal-Ligand Coordination Bonds as Transient Crosslinks.

Hydrogels that have both permanent chemical crosslinks and transient physical crosslinks are good model systems to represent tough gels. Such "dual-crosslink" hydrogels can be prepared either by simultaneous polymerization and dual crosslinking (one-pot synthesis) or by diffusion/complexation of the physical crosslinks to the chemical network (diffusion method). To study the effects of the preparation methods and of the crosslinking ratio on the mechanical properties, the equilibrium swelling of the dual-crosslink gels need to be examined. Since most of these gels are polyelectrolytes, their swelling properties are complex, so no systematic study has been reported. In this work, we synthesized model dual-crosslink gels with metal-ligand coordination bonds as physical crosslinks by both methods, and we proposed a simple way of adding salt to control the swelling ratio prepared by ion diffusion. Tensile and linear rheological tests of the gels at the same swelling ratio showed that during the one-pot synthesis, free radical polymerization was affected by the transition metal ions used as physical crosslinkers, while the presence of electrostatic interactions did not affect the role of the metal complexes on the mechanical properties.

Tuning Ligand-Coordinated Single Metal Atoms on TiO2 and their Dynamic Response during Hydrogenation Catalysis.

Ligand-coordinated supported catalysts (LCSCs) are of growing interest for heterogeneous single-atom catalysis. Here, the effect of the choice of organic ligand on the activity and stability of TiO2 -supported single-atom Pt-ligand catalysts was investigated for ethylene hydrogenation. The activity of these catalysts showed a significant dependence on the choice of ligand and also correlated with coordination number for Pt-ligand and Pt-Cl- . Of the three ligands examined in this study, the one with the lowest Pt coordination number, 1,10-phenanthroline-5,6-dione (PDO), showed the lowest reaction temperature and highest reaction rate, likely due to those metal sites being more accessible to reactant adsorption. In-situ X-ray absorption spectroscopy (XAS) experiments showed that the activity also correlated with good heterolytic dissociation of hydrogen, which was supported by OH/OD exchange experiments and was the rate-determining step of the hydrogenation reaction. In these in-situ XAS experiments up to 190 °C, the supported Pt-ligand catalyst showed excellent stability against structural and chemical change. Instead of Pt, the PDO ligand could be coordinated with Ir on TiO2 to form Ir LCSCs that showed slow activation by loss of Ir-Cl bonds, then excellent stability in the hydrogenation of ethylene. These results provide the chance to engineer ligand-coordinated supported catalysts at the single-atom catalyst level by the choice of ligand and enable new applications at relatively high temperature.

Zn2+-Imidazole Coordination Crosslinks for Elastic Polymeric Binders in High-Capacity Silicon Electrodes.

Recent research has built a consensus that the binder plays a key role in the performance of high-capacity silicon anodes in lithium-ion batteries. These anodes necessitate the use of a binder to maintain the electrode integrity during the immense volume change of silicon during cycling. Here, Zn2+-imidazole coordination crosslinks that are formed to carboxymethyl cellulose backbones in situ during electrode fabrication are reported. The recoverable nature of Zn2+-imidazole coordination bonds and the flexibility of the poly(ethylene glycol) chains are jointly responsible for the high elasticity of the binder network. The high elasticity tightens interparticle contacts and sustains the electrode integrity, both of which are beneficial for long-term cyclability. These electrodes, with their commercial levels of areal capacities, exhibit superior cycle life in full-cells paired with LiNi0.8Co0.15Al0.05O2 cathodes. The present study underlines the importance of highly reversible metal ion-ligand coordination chemistries for binders intended for high capacity alloying-based electrodes.

Supramolecular Porphyrin Nanostructures Based on Coordination-Driven Self-Assembly and Their Visible Light Catalytic Degradation of Methylene Blue Dye.

A series of porphyrin triads (1-4), in which each triad is composed of a Sn(IV) porphyrin and two free-base (or Zn(II)) porphyrins, was synthesized and their self-assembled nanostructures were studied. Depending on the substituent on porphyrin moieties, each triad was self-assembled into a different nanostructure. In particular, the cooperative coordination of 3-pyridyl groups in the Sn(IV) porphyrin with the axial Zn(II) porphyrins in triad 4 leads to forming uniform nanofibers with an average width of 10-22 nm. Other triads without the coordinating interaction between the central Sn(IV) porphyrin and the axial porphyrins formed irregularly shaped aggregates in contrast. The morphologies of nanofiber changed drastically upon the addition of pyrrolidine, in which pyrrolidine molecules break down the self-assembly process by coordinating with the axial Zn(II) porphyrins. All porphyrin aggregates exhibited efficient photocatalytic performances on the degradation of methylene blue dye under visible light irradiation. The degradation efficiencies after 2 h were observed to be between 70% and 95% for the aggregates derived from the four triads.

Bisphosphonate-based nanocomposite hydrogels for biomedical applications.

Nanocomposite hydrogels consist of polymeric network embedded with functional nanoparticles or nanostructures, which not only contribute to the enhanced mechanical properties but also exhibit the bioactivities for regulating cell behavior. Bisphosphonates (BPs) are capable of coordinating with various metal ions and modulating bone homeostasis. Thanks to the inherent dynamic properties of metal-ligand coordination bonds, BP-based nanocomposite hydrogels possess tunable mechanical properties, highly dynamic structures, and the capability to mediate controlled release of encapsulated therapeutic agents, thereby making them highly versatile for various biomedical applications. This review presents the comprehensive overview of recent developments in BP-based nanocomposite hydrogels with an emphasis on the properties of embedded nanoparticles (NPs) and interactions between hydrogel network and NPs. Furthermore, various challenges in the biomedical applications of these hydrogels are discussed to provide an outlook of potential clinical translation.

Synthesis of Double-Shelled Hollow Inorganic Nanospheres through Block Copolymer-Metal Coordination and Atomic Layer Deposition.

Double-shelled hollow (DSH) structures with varied inorganic compositions are confirmed to have improved performances in diverse applications, especially in lithium ion battery. However, it is still of great challenge to obtain these complex nanostructures with traditional hard templates and solution-based route. Here we report an innovative pathway for the preparation of the DSH nanospheres based on block copolymer self-assembly, metal-ligand coordination and atomic layer deposition. Polymeric composite micelles derived from amphiphilic block copolymers and ferric ions were prepared with heating-enabled micellization and metal-ligand coordination. The DSH nanospheres with Fe2O3 stands inner and TiO2 outer the structures can be obtained with atomic layer deposition of a thin layer of TiO2 followed with calcination in air. The coordination was carried out at room temperature and the deposition was performed at the low temperature of 80 °C, thus providing a feasible fabrication strategy for DSH structures without destruction of the templates. The cavity and the outer layer of the structures can also be simply tuned with the utilized block copolymers and the deposition cycles. These DSH inorganic nanospheres are expected to find vital applications in battery, catalysis, sensing and drug delivery, etc.